Determination of arsenic(III) for the investigation of the microbial oxidation of arsenic(III) to arsenic(V)

Recent evaluations of acute and chronical toxicity of arsenic resulted in a reduction of the standard value for total arsenic from 40 μg/L to 10 μg/L in drinking water which will be valid in Germany after a transition period as from January 1996. Arsenic is well known as substance of deep groundwaters, mainly of geogenic origin and normally found as As(III) or As(V). As(V) is well removable by flocculation and filtration after adding iron salts. As(III), however, has to be oxidized first to As(V). Therefore, it is important for treatment techniques to be able to distinguish between As(III) and As(V). A modified determination of As(III) using flow injection analysis was installed and optimized in order to investigate whether As(III) may be oxidized to As(V) by bacteria in natural waters. The results showed that at 4°C, no As(III)-oxidation was observed within 14 days. At room temperature, however, in the bacteria-containing samples, an As(III)-oxidation was found starting after 3 to 7 days. After 14 days, no As(III) was left over. In contrast, in the sterile samples, no As(III)-oxidation could be observed within 14 days. These results demonstrated that microbial processes influence the oxidation of As(III) to As(V) in natural waters.     

Isotopic study of alluvial groundwaters,south-west lockyer valley,queensland, australia

The isotopic chemistry of alluvial groundwaters from two adjacent valleys are described and hydrological processes within related aquifers are identified as evidenced by oxygen-¹⁸, deuterium, tritium and chloride data. A plot of δ¹⁸O against δD values reveals isotopic enrichment of the groundwater by the recycling of spray irrigation water. A plot of tritium versus chloride concentrations displays separate linear correlations for alluvial groundwaters within the two valleys. The salinity has a common source, therefore the separate correlations are interpreted as the past transfer of low salinity groundwater from the alluvial aquifers in one valley to the underlying sandstone aquifers.     

Radon variation in groundwaters in the Campi Flegrei Caldera (southern Italy) during and after the 1982–1984 bradyseismic crisis

Groundwater Rn concentration has been monitored at several sites in the Campi Flegrei Caldera since the time of the last episode of bradyseismic activity. The results concerning the period 1983–88 indicate that the Rn concentration is spatially variable due to the different chemico-physical characteristics of the waters or structural features. Rn concentration is generally influenced by the long-term changes of meteorological factors. Rainfalls appear to affect the Rn content of the most superficial aquifers. Several short-term spike-like Rn anomalies have been detected both during and after the period of the bradyseismic crisis. They do not show correlation with temporal changes of the pH and/or temperature of waters. A systematic correlation between Rn anomalies and episodic strong rainfall events is also absent. Furthermore, a clear relationship between Rn spikes and both uplift velocity changes and seismic activity has not been found.The overall evidence makes it very difficult to understand the temporal changes of groundwater Rn concentration that have occurred during and after the 1982–84 bradyseismic crisis. Nevertheless, a clear causal relationship between Rn concentration and the dynamics of the bradyseism is observed in some monitored sites. Its appearance may have been favoured by the low Rn concentration in the groundwaters during periods of quiescent activity.     

Groundwaters of Florence (Italy): Trace element distribution and vulnerability of the aquifers

Geochemical and hydrogeological research has been carried out on 109 wells in the alluvial plain of Florence, in order to evaluate conductivity and main chemistry of ground waters, the pattern of some possible pollutant chemical species (Fe, Mn, Cr, Cu, Pb, Zn, NO₂, NO₃), and the vulnerability of the aquifers. The plain is made up of Plio-Quaternary alluvial and lacustrine sediments for a maximum thickness of 600 m. Silts and clays, sometimes with lenses of sandy gravels, are dominant, while considerable deposits of sands, pebbles, and gravels occur along the course of the Arno river and its tributary streams, and represent the most important aquifer of the plain. The groundwaters analyzed belong to this aquifer or to the smaller ones, hosted in the gravel lenses. Most waters show conductivity values around 1000–1200 S, and almost all of them have an alkaline-earth-bicarbonate chemical character; these features are consistent with the mainly calcareous lithology of the aquifers. In the western areas a higher salt content of the groundwaters is evident, probably related to the presence of industrial activities which use water desalinators. Heavy metal and NO₂, NO₃ analyses point out that no important pollution phenomena affect the groundwaters; all the mean values of the chemical considered species are below the maximum admissible concentration (MAC) fixed by the European Community for drinkable waters. Nevertheless, some anomalies of NO₂, NO₃, Fe, Mn, and Zn are present in the plain. Apart from Mn, which seems to be released by certain calcareous gravels, the other anomalies have a local influence, since they disappear even in the nearest wells. The most plausible causes can be recognized in losses of the sewage system (NO₂=3–4 mg/t); use of nitrate compounds in agriculture (NO₃=60–70 mg/l); oxidation of well pipes (Fe 20 mg/l; Zn 6 mg/l). As regards Cr, Cu, and Pb, all the observations are below the MAC; therefore, the median values of < 3, 3.9, and 1.1 g/l, respectively, could be considered reference concentrations for groundwaters circulating in calcareous lithotypes, under undisturbed natural conditions. Finally, a map of vulnerability related to the most superficial and important aquifer has been elaborated on the basis of thickness and permeability of the covers. The map shows that the areas near the Arno river are highly vulnerable, for the minimum thickness (or lacking) of sediments covering the aquifer. On the other hand, in the case of pollution, several factors not considered in the map could significantly increase the self-purification capacity of the aquifer, such as the dilution of groundwaters caused by the feeding of the rivers, the bacteria oxidation of nitrogenous species, and the sorption capacity of clay minerals and organic matter with respect to trace metals.     

Geochemistry, genesis, and health implications of fluoriferous groundwaters in the upper regions of Ghana

 The most appropriate and widely used source of drinking water for the populations of the upper regions of Ghana is groundwater. In general, groundwater quality is acceptable except for some parts of the Bolgatanga and Bongo Districts, where there are occurrences of elevated levels of natural groundwater fluoride. Concentrations of groundwater fluoride in excess of the World Health Organization (WHO) maximum guideline value (1.5 mg/l) in the Bongo area have been known since 1978. However, the effect of fluoride on people ingesting the water did not receive public and medical attention until October 1993, when health personnel were asked to investigate the cause of stained teeth in school children. The investigation established that 62% of the total population of school children in the Bongo area had dental fluorosis. Against this background, a study was initiated to understand the geochemistry, genesis, and distribution of fluoride in relation to the geology of the area. Groundwater fluoride in the upper regions ranges from 0.11 to 4.60 ppm, with the highest concentrations associated with the fluorine-enriched Bongo coarse-grained hornblende granite and syenite suite. The source of groundwater fluoride within the Bongo granitoids is dissolution of the mineral fluorite and dissolution of and anion exchange with micaceous minerals and their clay products. Applying the WHO recommended guideline values for fluoride in drinking water reveals that 49% of wells in the area deliver water below the optimum level of 0.5 mg/l F^–; these populations are thus prone to dental caries. Twenty-eight percent of the wells fall within the optimum interval for good dental health (0.5–1.5 mg/l F^–). Twenty-three percent of the wells have concentrations above the recommended maximum guideline limit of 1.5 mg/l F^–; this population is susceptible to dental and possibly skeletal fluorosis. Climatic conditions of the area suggest that the individual water consumption is in the order of 3 to 4 l which is higher than the WHO estimate of 2 l/adult/day. In addition, dietary intake for the upper region population is probably higher than WHO baseline values (0.2–0.5 mg/day). This implies that a much higher population is susceptible to developing dental and skeletal fluorosis than originally suspected. Geochemical symbol plot maps help geochemists understand factors controlling the distribution and uptake of fluoride in the upper regions, but they are of minimal value to health officials responsible for planning epidemiological studies and dental health education programs in the region. By casting fluoride data into contoured 'geochemical health-risk maps' using intake interval guidelines more closely aligned to regional climatic and dietary conditions, health officals can better judge the impacts (regional and population based) of fluoride on segments of the population, such as various sex and age groups. Received: 11 March 1997 · Accepted: 17 June 1997     

Source and mobility of minor and trace elements in a volcanic aquifer system: Mt. Vulture (southern Italy)

In this paper we provide a geochemical investigation on 34 groundwater samples in the Mt. Vulture volcanic aquifer representing one of the most important groundwater resources of the southern Italy pumped for drinking and irrigation supply. The present study includes the first data on the abundance and mobility of minor and trace elements and the thermodynamic considerations on water–rock interaction processes in order to evaluate the conditions of alkali basalt weathering by waters enriched in magma-derived CO₂. The results highlight the occurrence of two hydrofacies: bicarbonate alkaline-earth and alkaline waters deriving from low-temperature leaching of volcanic rocks of Mt. Vulture, and bicarbonate-sulfate-alkaline waters (high-salinity waters) related to prolonged water circulation in alkali and feldspathoids-rich pyroclastic layers interbedded with clay deposits. The Al-normalized relative mobility (RM) of metals in Vulture's aquifer varies over a wide range (10^− 1 < RM < 10⁴), confirming that the basalt weathering is not a congruent and isochemical process. Chemical equilibrium studies show that the bicarbonate alkaline-earth and alkaline waters, having a short interaction with silicate minerals, plot very close to the kaolinite–smectite stability boundary, whereas the high-salinity waters fall in the stability field of smectite and muscovite because of prolonged interaction with alkali and feldspathoids-rich pyroclastic layers. Overall, for the bicarbonate alkaline-earth and alkaline waters, the release of toxic metals in solutions is related to the spatial variation of host-rock geochemistry, the high-salinity waters, collected near urban areas, show values higher than legal limits for Ni and As, likely as a consequence of anthropogenic contribution.     

Geochemistry of heavily exploited aquifers in the Emilia-Romagna region (Po Valley, northern Italy)

 More than 5 800 chemical analyses on water samples collected during 1987–1995 from 528 monitoring wells located in the southernmost part of the Po Valley (Emilia-Romagna region, northern Italy), one of the most urbanized, industrialized and agriculturally developed areas of Italy, have been processed. The analysis of data showed that: (1) waters are discharging from both confined and unconfined aquifers; (2) the water in the unconfined aquifer(s) is Ca(Mg)-HCO₃ in composition while confined ones are Na-Cl and/or Na-(HCO₃); (3) both confined and unconfined aquifer samples have δ¹⁸O and δD isotopic values of meteoric signature; (4) waters from both the aquifers are at least 40 years old; (5) the pumping rate has caused subsidence, particularly where the aquifer(s) is (are) unconfined; (6) the unconfined aquifer(s) is exposed to the risk of NO₃ pollution; (7) considering the present "pressure" (i.e. pumping rate) on this natural environment by human activity, care must be taken in the future to preserve this "strategic" resource. Received: 27 October 1997 · Accepted: 12 March 1998